Sublimation transfer dyeing with styryl dyes

ABSTRACT

1. IN THE PROCESS OF SUBLIMATION TRANSFER PRINTING FOR COLORING TEXTILE MATERIALS CONTAINING ACRYLIC FIBER, POLYESTER FIBER, OR MIXTURES THEREOF, THE IMPROVEMENT OF USING A STYRYL DYESTUFF WHICH SUBLIMES WITHIN A PERIOD OF 60 SECONDS AT 180 TO 200*C. AND WHICH HAS THE FORMULA   (NC)2-C=CH-(2-Y-CYCLOHEX-1,4-YLENE)-N(-R1)-R2   WHERE R1 AND R2 EACH IS HYDROGEN, AN UNSUBSTITUTED ALKYL GROUP OF 1 TO 8 CARBON ATOMS, OR AN ALKYL GROUP OF 1 TO 8 CARBON ATOMS SUBSTITUTED WITH HALOGEN, PHENYL, CYANO, ALKOXY, HYDROXY, ACYLOXY, ALKYLSULPHONYL, ALKYLCARBAMOYLOXY, PHENYLCARBAMOYLOXY, OR ALKYLOXYCARBONYLOXY, AND Y IS HYDROGEN OR METHYL.

United States Patent 9 US. Cl. 8-2.5 6 Claims ABSTRACT OF THE DISCLOSUREA process for dyeing and printing textile materials made of acrylicfibres and/ or polyester fibres, wherein the textile material is printedby the transfer printing process with a styryl dyestuff.

This is a continuation of application Ser. No. 843,184, filed July 18,1969, now abandoned.

It is known that prints on Woven or knitted textile fabrics can beproduced by printing a support material, usually paper, With an aqueousdispersion of a water- 3,846,069 Patented Nov. 5, 1974 ice It isadvantageous however, to use dyestuffs which sublime within a period of15 to seconds, but at most 60 seconds, at 180 to 210 C.

Suitable styryl dyestuffs are for example the dyestuffs of generalformula NC R1 wherein X is a sulphone, carboxylicacid ester, carboxylicacid amide or preferably, nitrile group, R and R each representshydrogen or a substituted or unsubstituted alkyl residue and A denotes apara-phenylene residue which may be substituted.

The groups R and R may be identical or different and can denote hydrogenatoms, or alkyl groups or substituted alkyl groups, for examplehalogenated alkyl groups, for example fl-chloroethyl,5,5,B-trifiuoroethyl or flyy-dichloropropyl groups, benzyl groups,fi-phenylethyl groups, fl-cyanoethyl groups, alkoxyalkyl groups forexample fl-ethoxyethyl or a-methoxybutyl groups, hydroxyalkyl groups forexample B-hydroxyethyl or 5,'y-dihydroxypropyl groups, acyloxyalkylgroups for example ,B-acetoxyethyl or 8,'ydiacetoxypropyl groups,B-alkylsulphonylalkyl insoluble dispersion dyestuff which can besublimed, and rsubsequently pressing the printed paper against the wovenor knitted textile fabric to be printed and heating to a temperature atwhich the dyestutf sublimes and passes over to the woven or knittedfabric so that the fabric is V dyed. Complicated patterns can be printedby means of this so-called transfer printing process without expensiveprinting machines being required at this stage.

Pure greenish-tinged yellow dyeings or prints have however not hithertobeen obtained in this way and this invention is based on the surprisingobservation that styryl dyestuffs which can be sublimed are particularlysuitable for transfer printing on acrylic fibres and especiallypolyester fibres and that particularly valuable greenish tinged yellowshades can thus be obtained.

The invention therefore provides a process for dyeing and printingtextile materials of acrylic fibres and especially polyester fibres,wherein the textile material is printed according to the transferprinting process with styryl dyestuffs, with or without other dyestuffs.

Sublimable dyestuffs within the scope of the invention are thosedyestuffs which according to the Process for the Determination of theDry Fixing'and Pleating Fastness of Dyeings and Prints (Dry Heat) of theSwiss Standards Association, Standard Specification SNV 95 833/ 1961,produce a surface bleeding (surface dyeing) which is adequate for dyeingpurposes. In Standard Specification SNV 95833/1961 a sample of the dyedmaterial is heated at certain test temperatures for 30 seconds inintimate contact with an undyed material for which the dyestuff has goodaffinity according to conventional dyeing methods, and under a pressureof 40 g.il0 g. per cmfi.

The definition according to the present invention however, also furtherincludes dyestuffs which after a heating time of up to 2 minutes and/orat a lesser contact pressure have adequately surface-bled on to (orsurfacedyed) the undyed textile material. It is immaterial whether thedyestuff sublimes in the physical sense provided it only passes in thegaseous state from one substrate to the other. A similar test to that inStandard Specification SNV 96855/ 1961 is described in the StandardSpecification of the American Association of Textile Chemists andColourists AATCC 117-1966T. In each case the direct contact of thematerial carrying the dyestuff with the undyed material is important.

groups for example B-methanesulphonylethyl or B-ethaneulphonylethylgroups, alkylcarbamoyloxyalkyl or arylcarbamoyloxyalkyl groups forexample fi-methylcarbamyloxyethyl groups, alkyloxycarbonyloxyalkylgroups for ex ample ,B-(methoxy, ethoxy or isopropoxy)-carbonyloxyethylgroups, B-benzoyloxyethyl groups or fi-(p-alkoxyorphenoxybenzoyl-oxy)-ethyl groups. The groups R and R in general shouldnot contain more than eight, and preferably not more than five carbonatoms.

Styryl dyestuffs which either possess an alkyl substituent on thephenylene ring and/or in which the group X represents a nitrile residueare particularly preferred.

As examples, the following dyestuffs may be mentioned:

Homologous series of dyestuffs with increasing fastness to sublimationare for example represented by the fatty acid esters of the monoordi-(B-hydroxyethyl) derivatives. Dyestuffs with the desired sublimationproperties can be obtained by varying the number of carbon atoms in thefatty acid residue.

In multi-colour printing by the transfer process the styryl dyestuffs tobe used according to the invention can be used together with otherdyestuffs which sublime in the same temperature range.

The printing ink carriers required for the transfer printing can be ofany desired structure based on cellulose, preferably non-textile, andpreferably two-dimensional, which is printed in the desired pattern withan aqueous or preferably at least partially organic printing ink;practically anhydrous organic printing inks are preferred. Paper isprincipally used as the printing ink carrier. The printing inks usuallycontain the dyestuff partially dissolved and partially as a finedispersion. Esters, ketones or alcohols, for example butyl acetate,acetone, methyl ethyl ketone, ethanol, isopropanol or butanol arepreferably used as solvents. The printing inks may contain thickeners.In aqueous inks water-soluble thickeners are used, for example polyvinylalcohol, carob bean flour, methylcellulose or water-solublepolyacrylates.

In the case of the preferred organic inks, easily soluble high molecularweight resins are used which have a softening point so high that theresins are not tacky during transfer printing; as resins, cellulosederivatives, for example the acetates or the ethyl, hydroxyethyl and/orhydroxypropyl ethers may be particularly mentioned.

In order to manufacture the printing inks, dyestuff preparations may beused which contain the above mentioned styryl dyestuffs and a resinwhich can be identical with the above mentioned thickeners or differenttherefrom. When it is different, it can also be a low molecular weightresin which does not cause any thickening effect and only serves toprevent agglomeration of the finely ground dyestuff. Preferably, theabove mentioned cellulose derivatives are used as the resin.

A series of further resins, solvents and other suitable additives ismentioned in Patent Application Ser. No. 743,287, filed July 9, 1968 byGuenther Zwahlen, now abandoned in favor of US. Ser. No. 99,678, filedDec. 18, 1970 as a continuation-in-part thereof, now abandoned in favorof US. Ser. No. 354,978, a continuation of the latter application, filedApril 27, 1973. In addition to the above-disclosed, preferred cellulosederivative resins, U.S. Ser. No. 743,287 discloses the followingeligibles resins:

(a) Colophony, and the derivative thereof in all forms, for example,hydrogenated, dimerized or polymerized, esterified with monohydric orpolyhydric alcohols, with resin-formers, for example, acrylic acid andbutanediol or maleic acid and pentaerythritol, modified colophony,calcium or zinc salts of colophony, abietic acid and the esters thereof.Soluble phenol resins modified with colo phony and resins based onacrylic compounds, and also other natural resins, for example, linseedoil varnish, shellac and other copals,

(b) Maleic resins, oil-free alkyd resins, styrolized alkyd resins,vinyltoluene-modified alkyd resins with synthetic fatty acids, linseedoil-alkyd resins, dehydrated castor oilalkyd resins, castor oil-alkydresins, soybean oil-alkyd resins, coconut oil-alkyd resins, talloil-alkyd resins, fish oil-alkyd resins and acrylic acid-modified alkydresins,

(c) Terpene resins,

(d) Polyvinyl resins, for example, polyvinylacetate, polyvinyl chlorideand polyvinylidene chloride, polyvinylacetals, polyvinyl alcohol,polyvinyl ether, copolymers and graft polymers with different vinylmonomers, polyacrylic acid resins, for example, acrylic acid esters andmethacrylic acid esters and the copolymers thereof,.

(e) Styrene polymers and copolymers,

(f) Polyolefines, for example, polyethylene and polyethylene wax,polypropylene and polypropylene wax, polybutylene, polyisobutylene,polyisoprene, substituted polyolefines, halogenated polyolefines and thecopolymers thereof, for example, ethylene and vinyl acetate copolymers,and other synthetic resins based on unsaturated hydrocarbons.

(g) Coumarone resins, indene resins and Coumaroneindene resins,

(l1) Aminoplasts, for example, urea and melamine resins, phenol resins,for example, novolaks (non-plasticized resols, resols modified withfatty acids or water-soluble resols); alkylphenol and arylphenol resins,terpenephenol resins, naphthaleneformaldehyde resins, carbamic acid andsulphatoamide resins, furan resins, ketone resins and aldehyde resins.

Also suitable are soluble polycondensation precursors, for example,phenol cresol, urea or melamine formaldehyde resins etherified withhigher alcohols, especially butyl alcohol, linseed oil-stand oil andwool oil-stand oil ester resins,

(i) Polyamide and polyester resins, for example, linear or branchedpolyester based on phthalic acid, adipic acid, sebacic acid and diols ordiol/triol mixtures and nylon 6, nylon 66 and isocyanate homopolymers,

(k) Cellulose derivatives of all kinds, for example, cellulose ethers,for example, methyl cellulose, hydroxyalkyl cellulose andalkylhydroxyalkyl cellulose, for example, hydroxyethyl cellulose orhydroxypropyl cellulose, cyanoethyl cellulose, ethyl cellulose andbenzyl cellulose in commercial form, and also nitrocellulose, which mayalso be hyponitrated. The corresponding derivatives of otherpolysaccharides may also be used, for example, derivatives of starch;

(1) Unvulcanized caoutchouc and derivatives thereof, for example,cyclocaoutchouc or chlorocaoutchouc and so forth,

(m) Non-cross-linked silicone resins,

(n) Polyurethanes (especially urethane primary products that do notharden until subjected to an elevated temmerature (o) Epoxy resins(especially resin-hardener mixtures and pre condensates thereof that donot harden until subjected to an elevated temperature), especially thosebased on bis-phenyl-A-diglycidyl ethers, and finally,

(p) Precursors of unsaturated polyester resins and dialkylphthalateprepolymers.

Suitable textile materials are particularly woven and knitted fabricsbut also fleeces, consisting of acrylic or acrylonitrile fibres,polyacrylonitrile fibres and copolymers of acrylonitrile and other vinylcompounds for example acrylic esters, vinyl chloride or vinylidenechloride, copolymers of dicyanethylene and vinyl acetate, as well as ofacrylonitrile block copolymers and especially of aromatic polyesterfibres, for example those consisting of terephthalic acid and ethyleneglycol or 1,4-dimethylolcyclohexane, and copolymers of terphthalic andisophthalic acid and ethylene glycol, as well as mixtures of thesefibres.

In the Example which follows, the parts denote parts by weight unlessotherwise specified.

EXAMPLE 20 Parts of the styryl dyestuff of formula (synthesizedaccording to British Patent Specification No. 458,405) are ground in alaboratory sandmill with 20 parts of hydroxypropylcellulose (trade nameKlucel J; Hercules) and 360 parts of water for 24 hours while cool ing.A loose yellow powder is obtained by spray drying.

2.5 Parts of the resulting powder, 2.5 parts of hydroxypropylcelluloseand 10 parts of isopropanol are stirred until the resin has completelydissolved and the dyestuff, to the extent that it does not dissolve, isuniformly distributed.

Paper is printed in a pattern with the resulting ink by the gravureprinting process, and is dried.

(NC)2C=CHO-N(CH3)2 (Ber. 35, 1320 (1920).)

ON CzH O O CC=CH (J. Chem. Eng. Data, 8, 597-599 (1963).)

We claim:

1. In the process of sublimation transfer printing for coloring textilematerials containing acrylic fiber, polyester fiber, or mixturesthereof, the improvement of using a styryl dyestulf which sublimeswithin a period of 60 seconds at 180 to 200 C. and which has the formulaNC R1 wherein R and R each is hydrogen, an unsubstituted alkyl group of1 to 8 carbon atoms, or an alkyl group of 1 to 8 carbon atomssubstituted with halogen, phenyl, cyano, alkoxy, hydroxy, acyloxy,alkylsulphonyl, alkylcarbamoyloxy, phenylcarbamoyloxy, oralkyloxycarbonyloxy, and Y is hydrogen or methyl.

2. The process of claim 1 wherein R and R each is hydrogen, methyl,ethyl, chloroethyl, cyanoethyl, hydroxyethyl, or acetoxyethyl.

3. The sublimation transfer printing process of claim 1 wherein thesublimable dyestutf is applied to a cellulosic transfer sheet andcontacted with the textile material under conditions of time,temperature, and pressure sufficient to cause the transfer of thedyestuff to the textile.

4. The process of claim 3 wherein the'transfer sheet is paper.

5. A transfer sheet for use in the sublimation transfer process whichcomprises a cellulosic support printed with at least one styryl dyestuifof the formula NC R1 wherein R and R each is hydrogen, an unsubstitutedalkyl group of 1 to 8 carbon atoms, or an alkyl group of 1 to 8 carbonatoms substituted with halogen, phenyl, cyano, alkoxy, hydroxy,carbalkoxy, acylamino, acyloxy, alkylsulphonyl, alkylcarbamoyloxy,phenylcarbamoyloxy, or alkyloxycarbonyloxy, and Y is hydrogen or methyl.

6. A transfer sheet according to claim 5 in which the styryl dyestuff isin admixture with a cellulose ether or ester.

References Cited FOREIGN PATENTS 1,223,330 10/1958 France 8-2.5

OTHER REFERENCES Colour Index, 2nd edition, pp. 3401-3402. Pub. by Soc.Dyers & Col., Parkshere, England, March 1970.

AATCC Manual, p. 122, Test Method 1171967.

Kellett: Textile Mercury & Argus, Aug. 22, 1958, pp. 267, 269, and 275.

DONALD LEVY, Primary Examiner US. Cl. X.R. 8176, 177, 179

1. IN THE PROCESS OF SUBLIMATION TRANSFER PRINTING FOR COLORING TEXTILEMATERIALS CONTAINING ACRYLIC FIBER, POLYESTER FIBER, OR MIXTURESTHEREOF, THE IMPROVEMENT OF USING A STYRYL DYESTUFF WHICH SUBLIMESWITHIN A PERIOD OF 60 SECONDS AT 180 TO 200*C. AND WHICH HAS THE FORMULA